Cation Overcrowding Effect on the Oxygen Evolution Reaction

Huang, Jun; Li, Mengru; Eslamibidgoli, Mohammad Javad; Eikerling, Michael; Groß, Axel

doi:10.1021/jacsau.1c00315

Cited by 77 publications

(78 citation statements)

References 90 publications

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“…The same cation overcrowding effect has recently also been applied to explain the cation effect on the oxygen evolution reaction. 49 Effects of CO 2 Pressure. CO 2 is involved not only in the electrochemical reactions (Steps 1−4), but also in the homogeneous reaction in eq 22.…”

Section: Reaction Environmentmentioning

confidence: 99%

“…It should be noted that cation effects are multifaceted in electrocatalysis, including, for instance, hydrolysis, promoter, and electric field effects. , Our analysis emphasizes the steric effect. The same cation overcrowding effect has recently also been applied to explain the cation effect on the oxygen evolution reaction …”

Section: Tuning the Location Reaction Environmentmentioning

confidence: 99%

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Electrochemical CO₂ Reduction at Silver from a Local Perspective

2021

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The electrochemical reduction of CO2 to chemical fuels and value-added chemicals is a viable pathway to store renewably generated electrical energy and to mitigate the negative impact of anthropogenic CO2 production. Herein, we study how the local reaction environment dictates the mechanism and kinetics of CO2 reduction to CO at an Ag electrode. The local reaction environment is determined using a hierarchical model that accounts for multistep reaction kinetics, specific surface charging state at a given electrode potential, and mass transport phenomena. The model reveals vital mechanistic insights into the reaction behavior. The increasing Tafel slope with overpotential is seen to be influenced by the surface charging relation and mass transport effects. In addition, the decrease of the CO current density at high overpotentials is found to be caused not only by the decrease in CO2 concentration due to mass transport, surface charge effects, and pH increase but also by lateral interactions between HCOOad, COOHad, and Had. Moreover, we explore how the electrolyte properties, including bicarbonate concentration, solvated cation size, and CO2 partial pressure, tune the local reaction environment.

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Section: Reaction Environmentmentioning

confidence: 99%

Section: Tuning the Location Reaction Environmentmentioning

confidence: 99%

Electrochemical CO₂ Reduction at Silver from a Local Perspective

2021

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“…But again, there is no fundamental reason to presuppose that the free energy difference Δ G ads ( T , U ,pH) with regard to bromide adsorption should be independent of any changes in pH. For example, recently a pH dependence has been found in the calculated activity of the oxygen evolution reaction β-NiOOH(0001) on the RHE scale, in agreement with the experiment . This pH dependence has been mediated by the explicit consideration of a pH-dependent electric double layer structure in the calculations.…”

Section: Discussionmentioning

confidence: 90%

Reversible vs Standard Hydrogen Electrode Scale in Interfacial Electrochemistry from a Theoretician’s Atomistic Point of View

Groß

2022

J. Phys. Chem. C

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It is a general notion in interfacial electrochemistry that the stability of adsorbate phases that only contain hydrogen atoms should be independent of the pH value of the electrolyte on the scale of the reversible hydrogen electrode, whereas the stability of adsorbate phases that do not contain any hydrogen should be independent of the pH value on the scale of the standard hydrogen electrode. In this Perspective, it will be argued on the basis of a grand-canonical approach that such a Nernstian behavior can only be reproduced if the free energy of the adsorbate phase is independent of the electrochemical control parameters. In general, this should not be true, so that the Nernstian behavior should be the exception rather than the rule. Still, structural and chemical factors will be discussed that might lead to a Nernstian behavior. This requires an analysis of the electrochemical electrolyte/electrode interface on the atomistic level. At the same time, this analysis also provides a guideline for the validity of grand-canonical simulations using the concept of the computational hydrogen electrode in which the dependence of the energy of adsorbate phases on pH and electrode potential is neglected.

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“…The concept of SWS dominated surface transient states to tune the concerted electron and proton enables optimization of the entire electrochemical interface as opposed to only catalysts structure to improve activity for the hydrogen evolution reaction, which is critical to designing more active electrochemical interfaces for energy storage and conversion reactions. This unique reaction mechanism may not only provide an important guidance for the design/selection of catalysts/electrolytes for the nanomaterial-catalyzed reactions in an aqueous environment, including CO 2 /CO reduction [85][86][87][88][89] , nitrogen reduction 17,90,91 , and other electrocatalytic reduction reactions 92 , but also shed new light on the nanoscale-range electron and proton transfer through the water-line 'bridge' in the biological macromolecule system [93][94][95] , which could follow the out sphere electron transfer model of Marcus theory with connected SWs as a bridge [96][97][98] . Author Contributions PYW and JFZ performed the main experiments and equally contribute to this research.…”

Section: Discussionmentioning

confidence: 99%

Activation of H2O tailored by interfacial electronic states at nanoscale interface for enhanced electrocatalytic hydrogen evolution

Zhang

Wang

Zhou

et al. 2022

Preprint

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Despite the fundamental and practical significance of the hydrogen evolution reaction (HER), the reaction kinetics at the molecular level is not clear, particularly in basic media. Here, with ZIF-67 derived Co-based carbon frameworks (Co/NC) as a model catalyst, we systematically investigated the effects of different reaction parameters on the HER kinetics, and surprise found that HER activity was not directly dependent on the type of nitrogen in the carbon framework, but on the relative content of surface hydroxyl and water (OH-/H2O) adsorbed on Co active sites embedded in carbon frameworks. When the ratio of the OH-/H2O was close to 1:1, Co/NC nanocatalyst showed the best reaction performance under the condition of high-pH electrolytes, e.g., with an overpotential of only 232 mV at a current density of 10 mA cm-2 in 1 M KOH electrolyte. We unambiguously identified that, the structural water molecules (SWs) in the form of hydrous hydroxyl complex absorbed on metal centers {OH-∙H2O@M+} were catalytic active sites for enhanced HER, where M+ could be transition and/or alkaline metal cations. Different from the traditional hydrogen bonding of water, the hydroxyl (hydroxide) groups and water molecules in SWs were mainly transiently bonded together through the spatial interaction between the p orbitals of O atoms, showing characteristics of delocalized π bond with dynamic feature. These new formed surface bonds or transient states could be a new weak interaction, which can act as an alternative channel for concerted electron and proton transfer at electrode surface. The capturing of new surface states not only answers pH-, cation- and transition metal- dependent hydrogen evolution kinetics, but also provides completely new insights into the understanding of other electrocatalytic reduction involved by other small moleculesm, including CO2, CO and N2 etc.

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Cation Overcrowding Effect on the Oxygen Evolution Reaction

Cited by 77 publications

References 90 publications

Electrochemical CO₂ Reduction at Silver from a Local Perspective

Electrochemical CO₂ Reduction at Silver from a Local Perspective

Reversible vs Standard Hydrogen Electrode Scale in Interfacial Electrochemistry from a Theoretician’s Atomistic Point of View

Activation of H2O tailored by interfacial electronic states at nanoscale interface for enhanced electrocatalytic hydrogen evolution

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Cation Overcrowding Effect on the Oxygen Evolution Reaction

Cited by 77 publications

References 90 publications

Electrochemical CO2 Reduction at Silver from a Local Perspective

Electrochemical CO2 Reduction at Silver from a Local Perspective

Reversible vs Standard Hydrogen Electrode Scale in Interfacial Electrochemistry from a Theoretician’s Atomistic Point of View

Activation of H2O tailored by interfacial electronic states at nanoscale interface for enhanced electrocatalytic hydrogen evolution

Contact Info

Product

Resources

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Electrochemical CO₂ Reduction at Silver from a Local Perspective

Electrochemical CO₂ Reduction at Silver from a Local Perspective